Catalyst for production of olefin polymers



United States Patent 3,152,989 (IATALYST FOR PRDDUCTIGN GE OLEFINPOLYMERS Gene Nowlin, Princeton, N.J., and Harold D. Lyons, Orange,Tern, assignors to Phillips Petroleum Company, a corporation of DelawareNo Drawing. Original application Dec. 39, 1955, Ser. No. 556,482, nowPatent No. 3,024,227, dated Mar. 6, 1562. Divided and this applicationGet. 13, 1961, Ser. No. 144,857

6 Claims. {Cl. 252-429) This invention relates to a novel catalyst foruse in a process for polymerizing olefins.

This application is a division of our copending application US. SerialNo. 555,482, filed December 30, 1955, now Patent 3,024,227 (March 6,1962).

Reactions for polymerizing olefins are well known in the art and aregenerally carried out in the presence of catalysts. One class ofcatalysts which has been used in the polymerization of monoolefins,particularly ethylene, is organornetal compounds, for exampletriethylaluminum, and the polymers which have been obtained inaccordance with this method are generally liquid or low molecular weightsolid polymers. Frequently, the polymers obtained are dimers or trimersof the olefin charged. However, it is often desired to produce highermolecular weight polymers which have desirable properties of heatstability and can be molded into vessels, pipes and tubing. Such usescannot be made of the lower molecular weight polymers, for example, apolymer having a molecular weight of about 1000, since a polymer of thismolecular weight is a wax-like material.

It is an object of this invention, therefore, to provide an improved andnovel catalyst for use in a process for the production of high molecularweight olefin polymers.

A still further object is to produce high molecular weight solidpolymers of olefins, such as ethylene.

Other and further objects and advantages of this invention will becomeapparent to those skilled in the art upon consideration of theaccompanying disclosure.

It has now been discovered that an unexpected improvement in theproduction of high molecular weight polymer is obtained when an olefin,such as ethylene, is polymerized in the presence of a catalystcomposition comprising (1) a metal halide selected from the groupconsisting of halides of titanium, zirconium, hafnium and germaninum (2)a peroxide corresponding to the formula R'OOR', wherein R is hydrogen,an alkyl, aralkyl, alkaryl, cycloalkyl, acyl, alkyne or aryl radical,and (3) at least one component selected from the following: (a) anorganometal halide corresponding to the formula R MX wherein R is asaturated acylic hydrocarbon radical, a saturated cyclic hydrocarbonradical, an aromatic hydrocarbon radical, or combination of theseradicals, wherein M is a metal selected from the group consisting ofaluminum, gallium, indium, thallium, and beryllium and wherein X is ahalogen, and wherein x and y are integers, the sum of x and y beingequal to the valence of the metal; (b) a mixture of an organic halideand at least one metal selected from the group consisting of sodium,potassium, lithium, rubidium, cesium, eryllium, magnesium, zinc,cadmium, mercury, aluminum, gallium, indium and thallium; and (c) acomplex hydride corresponding to the formula M'M"H wherein M is analkali metal, M" is a metal selected from the group consisting ofaluminum, gallium, indium and thallium, and m is equal to the sum of theValences of the two metals. The improvement obtained when polymerizingan olefin in the presence of our novel catalyst is, firstly, thatpolymers of much higher molecular weight possessing very high impactstrength and other desirable characteristics can be obtained than istrue when certain of the prior art catalysts have been employed, andsecondly, the polymerization reaction, particularly or ethylene, can beinitiated and carried out at considerably lower temperatures andpressures than are necessary when employing the catalysts and theprocesses of the prior art.

The metal halide component of our catalyst system comprises the halidesof the metals titanium, zirconium, hafnium and germanium. Examples ofmetal halides which can be used include titanium dichloride, titaniumtrichloride, titanium tetrachloride, titmum dibromide, titaniumtribromide, titanium tetrabromide, titanium diiodide, titaniumtriiodide, titanium tetraiodide, titanium trifluoride, titaniumtetrafluoride, zirconium dichloride, Zirconium trichloride, zirconiumtetrachloride, zirconium di bromide, zirconium tribromide, Zirconiumtetrabromide, zirconium tetraiodide, zirconium tetrafiuoride, hafniumtrichloride, hafnium tetrachloride, hafnium triiodide, hafniumtetraiodide, germanium dichloride, germanium trichloride, germaniumtetrachloride, germanium dibromide, germanium tetrabromide, germaniumdiiodide, germanium tetraiodide, germanium difluoride, germaniumtetrafluoride and the like. Mixtures of two or more of the metal halidescan be used in the catalyst system of our invention.

Irl admixture with one or more of the metal halides described above, ournovel catalyst comprises a peroxide corresponding to the formula ROOR,wherein R is hydrogen, an alkyl, aralkyl, alkaryl, cycloalkyl, acyl,alkyne, or aryl radical. These radicals may each contain from 1 to 20,inclusive, preferably not more than 10, carbon atoms. Examples ofperoxides which can be used include hydrogen peroxide, methylhydroperoxide, isopropyl hydroperoxide, tert-butyl hydroperoxide,cyclohexyl hydroperoxide, a,a-dimethyl-p-isopropylbenzyl hydroperoxide,dimethyl peroxide, di-n-propyl peroxide, di-tert-butyl peroxide, methylethyl peroxide, B-methyl-S-hydroperoxyl-butyne, Z-methyl-B-butynylhydroperoxide, bis(2-methyl-3-butynyl) peroxide, dibenzoyl peroxide,diacetyl peroxide, dipropionyl peroxide, a,a-dinaphthyl peroxide,peroxyformic acid, peroxyacetic acid, peroxybutyric acid, peroxybe-nzoicacid, peroxycinnamic acid, diperoxyterephthalic acid, and the like.

In admixture with at least one of the metal halides and at least one ofthe peroxides as set forth above our catalyst comprises at least oneorganometal halide corresponding to the formula R MX wherein R is asaturated acyclic hydrocarbon radical, a saturated cyclic hydrocmbonradical, an aromatic hydrocarbon radical, or mixtures of these radicals,wherein M is a metal selected from the group consisting of aluminum,gallium, indium, thallium and beryllium, and wherein X is a halogen. Thex and y are integers and the sum of x and y is equal to the valence ofthe metal M. X can be any of the halogens, including chlorine, bromine,iodine and fluorine. The saturated acyclic hydrocarbon radicals,saturated cyclic hydrocarbon radicals, and aromatic hydrocarbon radicalswhich can be substituted for R in the formula include hydrocarbonradicals having up to about 20 carbon atoms each. Radicals having 10carbon atoms or less are preferred since the resulting catalystcomposition has a greater activity for initiating the polymerization ofolefins. Mixtures of one or more of these-organometal halide components,such as a mixture of ethylaluminum dichloride and diethylaluminumchloride, can be used in our catalyst composition. Specific examples ofother organornetal halides is lithium aluminum hydride.

which are useful in the catalyst composition of this invention are thefollowing:

CH AICI (CH AlCl, C H AlCl z slz e sh a 1'r 2, '(c H-fl GaF, (C H GaCl(cyclohexane derivative), (C H )GaBr (benzene derivative), C H GaBr (C HGaF, (C H InCl (benzene derivative), C H InF (C H QInBr (cyclohexanederivative), C17H35B$L CH BeBr,

B-methylcyclohexylaluminum dichloride, 2-cyclohexy1- ethylgalliumdichloride, p-tolylberyllium iodide, di-(3- phenyl-l-methylpropyl)indiumfluoride, 2-(3-isopropylcyclohexyl)ethylthallium dibromide, and thelike.

Alternatively, or in addition to the R MX compounds set forth above, ourcatalyst comprises a mixture of one or more of the metal halides and oneor more of the peroxides described above and a mixture of an organichalide and a free or elemental metal. These organic halides includechloro-, bromo-, iodoand fluoro-substituted organic halides, and can bemono-, di-, trior tetrasubstituted organic halides. Within the broadclass of organic halides which is a component of our novel catalystcomposition, the 'class of halides defined as monohalogen-substitutedhydrocarbons having a maximum carbon chain length of not greater than 8carbon atoms are preferred since they are more easily handled in acommercial operation and are active to initiate the polymerization ofolefins in the catalyst composition of this invention. Still moredesirably, the organic halide which is used in the catalyst is a loweralkyl monohalide having a maximum carbon chain length of not greaterthan '8 carbon atoms. Examples of these organic halides which can beused in the catalyst are ethyl bromide, propylchloride, butyl iodide andpentyl fluoride. Other examples are 1,2-dibromoethane,1,3-dibromopropane, 1,2,3-tribromopropane, 1,2,3-trichloropropane,l,l-difluoroethane, and 1,4-diiodobutane. Other acyclic and cyclichalides as well as aromatic halides can be employed also. Examples ofthese are 1,3-dichlorocyclohexane, benzyl chloride, 1,4-dichlorobenzene,l- -bromodecane, l-chlorododecane, 2-chlorooctane, 2-chloro-4-methyloctane, cyclopentyl chloride, 1-chloro-3-phenylpropane,1-bromo-3-phenylhexane, cyclohexyl chloride and phenyl chloride. Also,alkenyl halides, such as allyl bromide, and alkynyl halides, such aspropargyl chloride, can be used. The metals which are employed inadmixture with an organic halide include one or more of so- .dium,potassium, lithium, rubidium, cesium, beryllium,

magnesium, zinc, cadmium, mercury, aluminum, gallium, indium, andthallium. The metals are usually used in the 'form of shavings, turningsor finelydivided powder. Various mixtures of combinations of theabove-mentioned organic halides and-metals can be employed in thecatalyst composition of this invention.

peroxides described above and a complex hydride correspending to theformula MM"H wherein M is an alkali metal, including sodium, potassium,lithium, rubidium and 'cesium, M" is a metal selected from the groupconsisting 'of aluminum, gallium, indium and thallium, and m is equal tothe sum of the valences of the two metals.

Examples of such complex hydrides arelithium aluminum hydride,

potassium aluminumhydride, sodium'aluminum hydride,

cesium aluminum hydride, sodium gallium hydride, lithiumthalliumhydride, lithium indium hydride, lithium gallium hydride,rubidium aluminum hydride, and the like. Thejpreferred member of thisclass of compounds Among thecatalyst compositions falling within thisdisclosure which are preferred because their use to catalyze thepolymerization of olefins provides relatively high molecular weightpolymers and/or permits the use of rela the process of this inventionare propylene, l-butene,'l-*

.be used, such as isobutylene.

tively low reaction temperatures and pressures are the following: amixture of titanium tetrachloride and benzoyl peroxide with anapproximately equimolar mixture of ethylaluminum dichloride anddiethylaluminum chloride; a mixture of zirconium tetrachloride andbenzoyl peroxide with an approximately equimolar mixture ofethylaluminum dichloride and diethylaluminum chloride; a mixture oftitanium tetrachloride, benzoyl peroxide and lithium aluminum hydride; amixture of titanium trichloride and benzoyl peroxide with anapproximately equimolar mixture of ethylaluminum dichlorideanddiethylaluminum chloride; a mixture of titanium tetrachloride anddi-tert-butyl peroxide with an approximately equimolar mixture ofethylaluminum dichloride and diethylaluminum chloride; and a mixture oftitanium tetrachloride, benzoyl peroxide, ethyl chloride and free orelemental sodium.

The amount of the catalyst composition of this invention which is usedin the polymerization of olefins can vary over a Wide range. Relativelysmall amounts of the catalyst provide the desired activating effect whenthe polymerization reaction is carried out as a batch process withcontinuous addition of the olefin as the polymerization reaction occurs.As much as 50 to 2000 grams of polymer can be obtained per gram ofcatalyst composi-' tion utilized in the reaction. When a continuous flowsystem is employed, the concentration of the total catalyst compositionis usually in the range from 0.01 weight percent to 1.0 weight percent,or higher.

The ratio of the amounts of peroxideto metal halide will generally be inthe range of 0.05 to 50, preferably 0.2 to 3 mols peroxide per mol ofmetal halide. The ratio of the amounts of organometal halide to metalhalide will usually be in the range of 0.05 to 50, preferably 0.2 to 3mols of organomental halide per mol of metal halide. 'The ratio of theamounts of organic halide, metal and metal halide will be in the rangeof 0.02 to 50 mols of the organic halide per mol of the metal halide andfrom.

0.02 to 50 mols of the metal per mol of the metal halide. A preferredratio is from 0.2 to 3 mols of organic halide per mol of metal halideand from 0.2 to 3 mols of metal per mol of the metal halide. The ratioof the amounts of the complex hydride to metal halide will generally bein the range of 0.05 to 50, preferably 0.2 to 3, mols of complex hydrideper mol of metal halide;

The materials which are polymerized with the novel catalyst compositionof this invention can be defined broadly as polymerizable hydrocarbons.Preferably, the polymerizable hydrocarbons are olefins containing a CH=C radical. The preferred class of polymerizable hydrocarbons used isaliphatic l-olefins having up to and includingS carbon atoms permolecule. Specifically, the normal l-olefin, ethylene, has been found topolymerize to a polymer thereof upon being contacted with the catalystcomposition of. this invention at lower tempertures and pressures thanhave been used in the processes of the prior are mentioned above.Examples of other polymerizable hydrocarbons which can be used in hexeneand l-octene. Branched chain olefins can also tuted and1,2-dialkyl-substituted ethylenes can also .be

used, such as butene-2, pentene-Z, hexene-2, heptene-3,2- Vmethylbutene-l, 2-methylhexene-l, Z-ethylheptene-l, and

the-like. Examples of the diand polyolefins in which the double bondsare in non-conjugated positions and which can be used in accordance withthis invention are 1,5-hexadiene, 1,4-pentadiene and 1,4,7-octatriene.Cyclic olefinscan also be used, such as cyclohexene. of the foregoingpolymerizable hydrocarbons can be po- Mixtures Also,1,l-dialkyl-substi-.

to a solid polymer in the process of this invention. This invention alsoapplicable to the polymerization of a monomeric material comprisingconjugated dienes containing from 4 to 8, inclusive, carbon atoms.Examples of conjugated dienes which can be used include 1,3-butadiene,2-methyl-l,3-butadiene, 2,3-dirnethyl-1,3-butadiene,2-rnethyl-1,3-pentadiene, chloroprene, l-cyanobutadiene, 2,3dimethyl-l,3-pentadiene, 2-methyl-3-ethyl-1,3-pentadiene,Z-methoxybutadiene, Z- henylbutadiene, and the like. It is within thescope of the invention to polymerize such conjugated dienes either aloneor in admixture with each other and/or with one or more other com poundscontaining an active CH =C group which are copolymerizable therewith.Included among these latter compounds are monoolefins such as thosedescribed hereinabove. Other examples of compounds containing an activeCH =C group which are copolymerizable with one or more conjugated dienesare styrene, acrylonitrile, methacrylonitrile, methacrylate, methylmethacrylate, vinyl acetate, vinyl chloride, Z-methyl-S-vinylpyridine,2- vinylpyridine, 4-viny1pyridine, etc.

One of the important advantages obtained in the polymerization ofolefins in the presence of our novel catalyst is that lower temperaturesand pressures can be used than in certain of the prior art processes.The temperature can be varied over a rather broad range, however, suchas from 250 F. and below to 500 F. and above. The preferred temperaturerange is from 50 to 300 F. Although pressures ranging from atmosphericand below up to 30,000 p.s.i.g. or higher can be employed, a pressurefrom atmospheric to 1000 p.s.i.g. is usually preferred with a pressurein the range of 100 to 700 p.s.i.g. being even more desirable.

In this connection, it is noted that it is preferred to carry out thereaction in the presence of an inert, organic diluent, preferably ahydrocarbon, with a pressure sufficient to maintain the diluent in theliquid phase, giving rise to a so-called mixer-phase system. However,the polymerization process of this invention proceeds in the gaseousphase without a diluent. The preferred pressure range set forth abovehas been found to produce solid polymers of olefins in excellent yields.

Suitable diluents for use in the polymerization process are paraffins,cycloparatfins and/ or aromatic hydrocarbons which are relatively inert,non-deleterious and liquid hexane and methylcyclohexane, and aromaticdiluents, under the conditions of the process. The lower molecularweight alkanes, such as propane, butane, and pentane are especiallyuseful when the process is carried out at low temperatures. However, thehigher molecular weight parafins and cycloparafiins, such as isooctane,cyclohexane and methylcyclohexane, and aromatic diluents, such asbenzene, toluene and the like, can also be used, particularly whenoperating at higher temperatures. Halogenated hydrocarbons, such ashalogenated aromatics, halogenated paraifms, halogenated cycloparaffinsand the like, are also useful as diluents. Mixtures of any two or moreof the above-named diluents can also be employed in the process of thisinvention.

The process utilizing the catalyst of this invention can be carried outas a batch process by pressuring the olefin into a reactor containingthe catalyst and diluent, if the latter is used. Also, the process canbe carried out continuously by maintaining the above-describedconcentrations of reactants in the reactor for a suitable residencetime. The residence time used in a continuous process can vary widely,since it depends to a great extent upon the temperature at which theprocess is carried out. The residence time also varies with the specificolefin that is polymerized. However, the residence time for thepolymerization of aliphatic monoolefins, within the preferredtemperature range of 50 to 300 F., falls within the range of one secondto an hour or more. In the batch process, the time for the reaction canalso vary widely, such as up to 24 hours or more.

In charging the catalyst components to the'reaction vessel, it ispreferred to operate so as to ensure that the peroxide is not present inthe reaction vessel with the organometal halide, the mixture of anorganic halide and a metal and/ or the complex hydride unless the metalhalide'is also included in the reaction mixture. In this regard it isdesirable to mix the metal halide and the peroxide before charging or tocharge these two components simultaneously.

It has been found that various materials in some instances may have atendency to inactivate the catalyst compositions of this invention.These materials include carbon dioxide, oxygen and water. Therefore, itis usually desirable to free the polymerizable hydrocarbon from thesematerials, as well as from other materials which may tend to inactivatethe catalyst before contacting the hydrocarbon with the catalyst. Any ofthe known means for removing such contaminants can be employed. When adiluent is used in the process, this material should generally be freedof contaminants, such as water, oxygen, and the like. It is desirable,also, that air and moisture be removed from the reaction vessel beforethe reaction is carried out. However, in some cases small amounts ofcatalyst inactivating materials, such as oxygen or water, can betolerated in the reaction mixture while still obtaining reasonably goodpolymerization rates. It is to be understood that the amount of suchmaterials present in the reaction mixture shall not be suflicient tocompletely inactivate the catalyst.

At the completion of the polymerization reaction, any excess olefin isvented and the contents of the reactor, including the solid polymerswollen with diluent, are then treated to inactivate the catalyst andremove the catalyst residues. The inactivation of the catalyst can beaccomplished by washing with an alcohol, water or other suitablematerial. In some instances, the catalyst inactivating treatment alsoremoves a major proportion of the catalyst residues while in other casesit may be necessary to treat the polymer with an acid, base or othersuitable material in order to effect the desired removal of the catalystresidues. The treatment of the polymer may be carried out in acomminution zone, such as a Waring Blendor, so that a finely dividedpolymer is thereby provided. The polymer is then separated from thediluent and treating agents, e.g., by decantation or absorption, afterwhich the polymer is dried. The diluent and treating agents can beseparated by any suitable means, e.g., by fractional distillation, andreused in the process.

A more comprehensive understanding of the invention may be obtained byreferring to the following illustrative examples which are not intended,however, to be unduly limitative.

EXAMPLE I Ethylene was polymerized in a 2700 cubic centimeter stainlesssteel reactor in accordance with the procedure described hereinbelow.

Two and forty-two hundredths grams (0.01 mol) of benzoyl peroxide wasadded to cubic centimeters of benzene (dried over sodium and distilled)to which had been added 0.949 gram (0.005 mol) of titaniumtetrachloride. The color of the titanium tetrachloride-benzene mixturewas yellow until the benzoyl peroxide was added, at which time the colorturned dark brown. This mixture was refluxed for twenty minutes underpurified nitrogen, at which time the color was noted to be a very darkorange brown. This mixture was then added to the reactor under purifiednitrogen pressure along with an additional 380 cubic centimeters ofbenzene. Four cubic centimeters of ethylaluminum sesquichloride,prepared as described hereinbelow, was mixed with 20 cubic centimetersof benzene and then added to the reactor. The reactor was then placed ina rocker and pressured with ethylene to 300 p.s.i.g. An electric heaterattached to the reactor was used to maintain the temperature at 300 F.Ethylene was pressured into the reactor from time to time as thereaction progressed and the temperature decreased. After hours and-52minutes, the reactor was 'repressured to 550 p.s.i.g. with ethylene. Thereaction was allowed to continue overnight, and after an overallreaction time of 16 /2 hours, the reactor was cooled and then opened. Adark brown polymer was recovered which immediately turned white uponcontact with methyl alcohol. The polymer was placed in a Waring Blendoralong with about 500 cubic centimeters of methyl alcohol andcomminuted-at speeds ranging from 8000 to 16,000 r.p.m. The polymer wasthen filtered and placed on porcelain dishes in a vacuum oven and driedfor 24 hours at 75 C. Approximately 50 grams of polymer were obtained.

The properties of a sample of the ethylene polymer produced as describedabove are presented below in Table I.

Table I Molecular weight (based on melt index) 38,575 Density, gms./cc.at room temperature 0.960 Flexibility Good Irnpact strength (fallingball method) 72 Melt index 1.198 Melting point, F. 2511-2 MoldabilityGood EXAMPLE H Ethylene was polymerized in a 1400 cubic centimeterstirred reactor following the procedure described hereinbelow.

In this example, 2.42 grams of benzoyl peroxide, 0.949 gram of titaniumtetrachloride and 4 cubic centimeters of ethylaluminum sesquichloride,prepared as described hereinbelow, were charged to the reactor whichcontained 400 cubic centimeters of cyclohexane (dried over sodium anddistilled). 'After all of the catalyst components were charged, ethylenewas pressured into the reactor until a pressure of 300 p.s.i.g, at 100F. was reached. The heating unit with which the reactor was supplied wasstarted, and it was noted that the reaction started almost immediatelyas evidenced by the drop in reactor pressure and the accompanyingtemperature rise. During the polymerization, the maximum temperaturereached was 300 F. After '50 minutes, the reactor was again pressuredwith ethylene to 300 p.s.i.g. The reactor was repressured on two otheroccasions, namely, one 7 minutes after the first repressuring andanother 30 minutes later. The heat source was removed 45 minutes afterthe last time the reactor was repressured, and the reactor then al- 'anddried overnight in avacuum oven maintained at The properties of a sampleof the ethylene polymer produced as described above are presented belowin Table. 11.

a Table II Molecular weight (based on inherent viscosity) 35,964Density, gms./cc. at room temperature 0.957 Impact strength (fallingball method) g 48" Melting point, F. 246:3 Inherent viscosity 1.471

The inherent viscosity was obtained at 130 C., using a solution of 0.2gram of polymer per 100 milliliters of tetralin.

EXAMPLE 111 Ethylene was polymerized in a 1200 cubic centimeterstainless, steel rocking autoclave in the presence of a catae-lyst..consisting of a mixture of 3.55 grams of titanium,

inactivate the catalyst.

tetrachloride and 4 grams of a mixture of diethylaluminum chloride andethylaluminum dichloride. ture of diethylaluminum chloride andethylaluminum dichloride was prepared in accordance with the proceduredescribed hereinafter. cubic centimeters of benzene (dried over sodium)and charged to the autoclave while maintaining the autoclave under anitrogen atmosphere. The ethylene was passed through a purificationsystem to remove oxygen, carbon dioxide and water vapor prior toentering the autoclave. The purification system comprised a pyrogallolsolution, a sodium hydroxide solution and drying agents. The ethylenewas charged to the autoclave while maintaining the catalyst and diluentat atmospheric temperature. The polymerization of the ethylene wasimmediately initiated, and as the addition of ethylene continued thetemperature of the reaction mixture increased rapidly to 175 F. Theethylene was passed into the autoclave as rapidly as the limitations ofthe purification system would permit. Maximum pressure reached in theautoclave was 300 p.s.i.g. At the end of a 15 minute reaction period,the bomb was opened, and a polymer of ethylene was present as asuspension in the benzene solution. One hundred cubic centimeters ofbutyl alcohol was added to the autoclave to The solid polymer wasfiltered from the benzene-alcohol mixture and then washed with isopropylalcohol. After filtering the polymer from the isopropyl alcohol, it isdried overnight in a vacuum oven at about 140 F. About grams ofpolyethylene was obtained.

The properties of a sample of the ethylene polymer produced as describedabove are presented below in Table III.

Table III Molecular weight (based on melt index) 9,025. Density, grams/cc. at room temperature 0.941. Flexibility Quite brittle. Impactstrength (falling ball method) Broke at 6". Melt index 445.0. Meltingpoint, 'F 242:2. Inherent viscosity 0.451. Color Light tan.

The mixture of diethylaluminum chloride and ethylaluminum dichloride wasprepared by placing 150 grams of aluminum shavings in a flask fittedwith a reflux condenser and heated to about 70 C. A trace of iodine wasadded to the flask to act as a catalyst, and ethyl chloridewas chargedto the flask in liquid phase. The temperature of the reaction mixturewas maintained in the range of to C. during the addition of the ethylchloride, and the reaction mixture was maintained under a nitrogenatmosphere. When substantially all ofthe aluminum shavings had reactedwith the ethyl chloride, the liquid product was removed from the flaskand fractionally distilled at 4.5 millimeters of mercury pressure in apacked distillation column. The distillate, boiling at 72 to 74 C. at4.5 millimeters of mercury pressure, was used in the catalystcompositions of Examples 1, II and III in the amount specifiedhereinabove. This fraction boiling at 72 to 74 C. was analyzed and foundto contain 47.4 weight percent chlorine. The theoretical chlorinecontent'for an equimolar mixture of diethylaluminum chloride andethylaluminum dichloride is 43 weight percent.

From a consideration of the data shown in Tables I,

II and III, it is seen that the addition, of benzoylperoxide to thecatalyst composition consisting of titanium tetration have utility inapplications where solid plastics are The mix- The catalyst wasdissolved in 500' and they can be molded to form articles of any desiredshape, such as bottles and other containers for liquids. Furthermore,they can be formed into pipe by extrusion.

As will be evident to those skilled in the art, many variations andmodifications can be practiced within the scope of the disclosure andclaims of this invention.

We claim:

1. A catalyst composition which forms on mixing materials comprising (1)a metal halide selected from the group consisting of halides oftitanium, zirconium, hafnium and germanium, (2) a peroxide correspondingto the formula ROOR, wherein R is a member selected from the groupconsisting of hydrogen, alkyl, aralk-yl, alkaryl, cycloalkyl, acyl,alkyne and aryl radicals, and (3) an organornetal halide correspondingto the formula R MX wherein R is a member selected from the groupconsisting of a saturated acyclic hydrocarbon radical, a saturatedcyclic hydrocarbon radical, an aromatic hydrocarbon radical andcombinations of these radicals, M is a metal selected from the groupconsisting of aluminum, gallium, indium, thallium and beryllium, and Xis a halogen, and wherein x and y are integers, the sum of x and y beingequal to the valence of the metal M, the amount of said peroxide beingin the range of 0.05 to 50 mols per mol of said metal halide and theamount of said organometal halide being in the range of 0.05 to 50 molsper mol of said metal halide.

2. A catalyst composition in accordance with claim 1 wherein the amountof said peroxide is in the range of 0.2 to 3 mols per mol of said metalhalide and the amount of said organometal halide is in the range of 0.2to 3 mols per mol of said metal halide.

3. A catalyst composition which forms on mixing materials consistingessentially of titanium tetrachloride, benzoyl peroxide, and anapproximately equimolar mixture of ethylaluminum dichloride anddiethylaluminum chloride, the amount of said benzoyl peroxide being inthe range of 0.05 to 50 mols per mol of said titanium tetrachloride andthe amount of said equimolar mixture being in the rangeof 0.05 to molsper mol of said titanium tetrachloride.

4. A catalyst composition which forms on mixing materials consistingessentially of Zirconium tetrachloride, benzoyl peroxide, and anapproximately equimolar mixture of ethylaluminum dichloride anddiethylaluminum chloride, the amount of said benzoyl peroxide being inthe range of 0.05 to 50 mols per mol of said zirconium tetra chlorideand the amount of said equimolar mixture being in the range of 0.05 to50 mols per mol of said zirconium tetrachloride.

5. A catalyst composition which forms on mixing materials consistingessentially of titanium trichloride, ben zoyl peroxide, and anapproximately equimolar mixture of ethylaluminum dichloride anddiethylaluminum chlo ride, the amount of said benzoyl peroxide being inthe range of 0.05 to 50 mols per mol of said titanium trichloride andthe amount of said equimolar mixture being in the range of 0.05 to 50mols per mol of said titanium trichloride.

6. A catalyst composition which forms on mixing materials consistingessentially of titanium tetrachloride, ditert-butyl peroxide, and anapproximate equimolar mixture of ethylaluminum dichloride anddiethylalurninum chloride, the amount of said di'tert-butyl peroxidebeing in the range of 0.05 to 50 mois per mol of said titaniumtetrachloride and the amount of said equimolar mixture being in therange of 0.05 to 50 mols per mol of said titanium tetrachloride.

References Cited in the file of this patent UNITED STATES PATENTS2,482,877 Schmerling Sept. 27, 1949 2,762,791 Pease et al Sept. 11, 19562,822,357 Brebner et a1. Feb. 4, 1958 2,905,645 Anderson et a1 Sept. 22,1959

1. A CATALYST COMPOSITION WHICH FORMS ON MIXING MATERIALS COMPRISING (1)A METAL HALIDE ASELECTED FROM THE GROUP CONSISTING OF HALIDES OFTITANIUM, ZIRCONIUM, HAFNIUM AND GERMANIUM, (2) A PEROXIDE CORRESPONDINGTO THE FORMULA R''OOR'', WHEREIN R'' IS A MEMBER SELECTED FROM THE GROUPCONSISTING OF HYDROGEN, ALKYL, ARALKYL, ALKARYL, CYCLOALKYL, ACYL,ALKYNE AND ARYL RADICALS, AND (3) AN ORGANOMETAL HALIDE CORRESPONDING TOTHE FORMULA RXMXY, WHEREIN R IS A MEMBER SELECTED FROM THE GROUPCONSISTING OF A SATURATED ACYCLIC HYDROCARBON RADICAL, A SATURATEDCYCLIC HYDROCARBON RADICAL, AN AROMATIC HYDROCARBON RADICAL ANDCOMBINATIONS OF THESE RADICALS, M IS A METAL SELECTED FROM THE GROUPCONSISTING OF ALUMINUM, GALLIUM, INDIUM, THALLIUM AND BERYLLIUM, AND XIS A HALOGEN, AND WHEREIN X AND Y ARE INTEGERS, THE SUM OF X AND Y BEINGEQUAL TO THE VALENCE OF THE METAL M, THE AMOUNT OF SAID PEROXIDE BEINGIN THE RANGE OF 0.05 TO 50 MOLS PER MOL OF SAID METAL HALIDE AND THEAMOUNT OF SAID ORGANOMETAL HALIDE BEING IN THE RANGE OF 0.05 TO 50 MOLSPER MOL OF SAID METAL HALIDE.